Description: This paper presents a synthesis of data from X-ray diffraction analyses of clay minerals and X-ray fluorescence analyses of bulk mudstones from Ocean Drilling Program Site 808. The samples come from three closely spaced holes drilled through the toe of the Nankai accretionary prism offshore Shikoku, Japan. Detrital assemblages of clay minerals are unusually uniform throughout the Nankai trench-wedge facies. Illite is the most abundant detrital clay mineral, followed by chlorite, smectite, and traces of kaolinite. Relative percentages of smectite increase within the upper subunit of the Shikoku Basin stratigraphy. This subunit contains abundant layers of volcanic ash, and the corresponding change in clay mineralogy probably was caused by synvolcanic weathering in source areas during the Pliocene, together with in-situ alteration of disseminated glass shards within the Shikoku Basin. At a depth of ~555 mbsf, the detrital and/or authigenic smectite component begins its transformation to illite/smectite mixed-layer clay. With increasing depth below this horizon there is a monotonic increase in illite interlayers. The onset of illitization occurs at an estimated temperature of ~65°C. Ordered (R = 1) illite/smectite interlayering first appears at depths of ~1220 mbsf (〈2-µm size fraction) and ~1100 mbsf (〈0.2-µm size fraction). The depth interval of the smectite-to-illite transformation coincides with a reduction in pore-water chlorinity; however, the absolute abundance of smectite appears to be insufficient to account for the changes in aqueous chemistry via in-situ dehydration reactions. Instead, significant volumes of diluted pore water probably were transported to Site 808, either from sources located deeper in the accretionary prism (where bulk mudstone porosities are lower) or from lateral sources where mudstones originally deposited in the Shikoku Basin may contain higher percentages of smectite. Significantly, we did not detect any anomalies in clay mineralogy or clay-mineral diagenesis within or near the décollement zone (945-964 mbsf). X-ray fluorescence analyses show that hemipelagic muds and mudstones at Site 808 are chemically uniform throughout most of the section. There are no geochemical perturbations, for example, within the décollement zone. Data from interbeds of volcanic ash demonstrate that the chemical effects of mud/ash dissemination and/or in-situ alteration of pyroclastic material are limited. In addition, ash layers are chemically heterogeneous within Unit III and Subunit IVa, which indicates that tephra was transported from a variety of andesitic to rhyolitic sources on the Japanese Islands during the Pliocene. In contrast, Miocene rocks of Unit V display a clear chemical divergence (little mixing) between rhyolitic tuffs and interbeds of multicolored mudstone. The most significant geochemical anomaly at Site 808 occurs well below the décollement zone between 1087 and 1111 mbsf. Variegated mudstones in this interval contain unusually high ratios of MgO/Al2O3, Fetotal/Al2O3, MnO/Al2O3, and CaO/Al2O3, together with high concentrations of Ba, Y, Sr, La, and Ce. We attribute this anomaly to hydrothermal alteration and/or precipitation of Ca-carbonate, siderite, barite, and related minerals, but we do not know when the event occurred. Fluid migration may have taken place during late Miocene time early in the depositional history of Shikoku Basin (i.e., above newly formed oceanic lithosphere) or during the Holocene as fluids advected through the Nankai accretionary prism.